Solids suspension with nanoparticle-associated viscoelastic surfactant micellar fluids

ABSTRACT

An aqueous, viscoelastic fluid gelled with a viscoelastic surfactant (VES) may suspend solids such as proppants, gravel, drilling debris, waste solids and the like with an effective amount of a nano-sized additive including, but not necessarily limited to alkali earth metal oxides, alkali earth metal hydroxides, alkali metal oxides, alkali metal hydroxides, transition metal oxides, transition metal hydroxides, post-transition metal oxides, and post-transition metal hydroxides. The additives may also reduce the amount of VES required to maintain a given viscosity. These viscoelastic surfactant gelled aqueous fluids may be used as treatment fluids for subterranean hydrocarbon formations, such as in hydraulic fracturing, gravel packing and the like. The magnesium oxide, zinc oxide or other nanometer scale-sized additives are at a scale that may provide unique particle charges that use chemisorption, crosslinking and/or other chemistries to associate the micelles and suspend the solids.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No. 12/042,439filed Mar. 5, 2008, issued as U.S. Pat. No. 9,556,376 on Jan. 31, 2017,which in turn is a continuation-in-part application of U.S. Ser. No.11/849,820 filed Sep. 4, 2007, issued as U.S. Pat. No. 8,278,252 on Oct.12, 2012, which in turn claims the benefit of U.S. Provisional PatentApplication 60/845,916 filed Sep. 20, 2006, and is acontinuation-in-part application of U.S. Ser. No. 11/125,465 filed May10, 2006 issued as U.S. Pat. No. 7,343,972 on Mar. 18, 2009, which inturn claims the benefit of U.S. Provisional Patent Application60/570,601 filed May 13, 2004, and is a continuation-in-part applicationof U.S. Ser. No. 11/755,581 filed May 30, 2007, issued as U.S. Pat. No.7,550,413 on Jun. 23, 2009, which in turn claims the benefit of U.S.Provisional Patent Application 60/815,693 filed Jun. 22, 2006.

TECHNICAL FIELD

The present invention relates to aqueous fluids gelled with viscoelasticsurfactants used during hydrocarbon drilling and recovery operations,and more particularly relates, in one non-limiting embodiment, tomethods and additives for suspending solids in such viscoelasticsurfactant-gelled aqueous fluids.

BACKGROUND

Hydraulic fracturing is a method of using pump rate and hydraulicpressure to fracture or crack a subterranean formation. Once the crackor cracks are made, high permeability proppant, relative to theformation permeability, is pumped into the fracture to prop open thecrack. When the applied pump rates and pressures are reduced or removedfrom the formation, the crack or fracture cannot close or healcompletely because the high permeability proppant keeps the crack open.The propped crack or fracture provides a high permeability pathconnecting the producing wellbore to a larger formation area to enhancethe production of hydrocarbons.

The development of suitable fracturing fluids is a complex art becausethe fluids must simultaneously meet a number of conditions. For example,they must be stable at high temperatures and/or high pump rates andshear rates which may cause the fluids to degrade and prematurely settleout the proppant before the fracturing operation is complete. Variousfluids have been developed, but most commercially used fracturing fluidsare aqueous based liquids which have either been gelled or foamed. Whenthe fluids are gelled, typically a polymeric gelling agent, such as asolvatable polysaccharide is used, which may or may not be crosslinked.The thickened or gelled fluid helps keep the proppants within the fluidduring the fracturing operation.

While polymers have been used in the past as gelling agents infracturing fluids to carry or suspend solid particles in the brine, suchpolymers require separate breaker compositions to be injected to reducethe viscosity. Further, the polymers tend to leave a coating on theproppant even after the gelled fluid is broken, which coating mayinterfere with the functioning of the proppant. Studies have also shownthat “fish-eyes” and/or “microgels” present in some polymer gelledcarrier fluids will plug pore throats, leading to impaired leakoff andcausing formation damage. Conventional polymers are also either cationicor anionic which present the disadvantage of likely damage to theproducing formations and the conductivity of propped fractures.

Aqueous fluids gelled with viscoelastic surfactants (VESs) are alsoknown in the art. VES-gelled fluids have been widely used asgravel-packing, frac-packing and fracturing fluids because they exhibitexcellent rheological properties and are less damaging to producingformations than crosslinked polymer fluids. VES fluids are also used asacid diverting, water and/or gas control fluids. VES fluids arenon-cake-building fluids, and thus leave no potentially damaging polymercake residue.

It has been discovered that alkaline earth metal oxides, alkaline earthmetal hydroxides, transition metal oxides, transition metal hydroxides,and mixtures thereof, and in particular magnesium oxide may serve toinhibit or prevent fluid loss in aqueous fluids gelled with VESs, asdescribed in U.S. patent application Ser. No. 11/755,581 filed May 30,2007 (U.S. Patent Application Publication No. 2008/0060812 A1),incorporated herein in its entirety by reference. Some of these samematerials may also be effective as system stabilizers and performanceenhancers for aqueous fluids gelled with VESs, as described in U.S.patent application Ser. No. 11/125,465 (U.S. Patent ApplicationPublication No. 2005/0252658 A1), also incorporated herein in itsentirety by reference.

It would be desirable if a method and/or composition would be devised tosuspend solids such as proppants, gravel, drilling debris, etc., evenmore effectively in viscoelastic surfactant gelled aqueous fluids.

SUMMARY

There is provided, in one form, a method for suspending solids in agelled aqueous fluid that involves adding to an aqueous base fluid thefollowing components in any order: a viscoelastic surfactant (VES)gelling agent, a particulate additive, and solids. The particulateadditive is present in an amount effective to suspend the solids in thegelled aqueous fluid. The particulate additive has a mean particle sizeof from about 1 to about 500 nm and may include, but not necessarily belimited to, alkali earth metal oxides, alkali earth metal hydroxides,alkali metal oxides, alkali metal hydroxides, transition metal oxides,transition metal hydroxides, post-transition metal oxides, andpost-transition metal hydroxides, and mixtures thereof. The solids mayinclude, but not necessarily be limited to, proppants, gravel, drillingdebris, waste solids, and combinations thereof.

There is additionally provided in another non-limiting embodiment agelled aqueous fluid that includes an aqueous base fluid, a viscoelasticsurfactant (VES) gelling agent, a particulate additive, and solids. Theparticulate additive may have a mean particle size of from about 1 nm toabout 500 nm or less. Suitable particulate additives include, but arenot necessarily limited to, alkali earth metal oxides, alkali earthmetal hydroxides, alkali metal oxides, alkali metal hydroxides,transition metal oxides, transition metal hydroxides, post-transitionmetal oxides, and/or post-transition metal hydroxides. The solidsinclude, but are not necessarily limited to, proppants, gravel, drillingdebris, and/or waste solids. The particulate additive is present in anamount effective to suspend the solids in the viscoelastic surfactantgelled aqueous fluid.

The particulate additives, also referred to herein as suspension agents(e.g. magnesium oxide (MgO) and/or magnesium hydroxide (Mg(OH)₂), andthe like), appear to improve the ability of VES micelle structures tosuspend solids, even when heated, that is, the VES fluid viscosity ismore stable over time even as fluid temperature is increased. Thesuspension agents have utility over a broad range of temperature ofabout 180° F. to about 300° F. (about 82° C. to about 149° C.). In manycases, clean-up of VES fluids may be improved by use of nano sizeparticulate additives that may be much smaller than the pores andpore-throat passages within a hydrocarbon reservoir, thereby beingnon-pore plugging particles that are easier to be removed and lessdamaging to the reservoir permeability, relative to using polymers.Additionally, the viscosity stability of the VES fluid may be furtherimproved by use of nano-sized particles that are able to stay within theVES fluid and travel where the VES fluid goes, including any fluid whichis leaked-off, that is, any VES fluid that invades and enters thereservoir pores during a treatment, such as during a gravel-pack,frac-pack, hydraulic frac, removing drilling debris in a drillingoperation, disposing of particulate solid waste in a fluid at highsolids loading, and the like. Since the nano-sized particulate additivesstay within the VES fluid, they thereby continue to stabilize theviscosity of any leaked-off VES fluid. This is in contrast to largersize particulate additives that become bridged-off (i.e. which plate outand are left upon the reservoir face and prevented from entering thereservoir pores with the VES fluid), including VES stabilizer agentsthat are larger than about 500 to 1000 nanometers in size.

The addition of alkali metal oxides, such as lithium oxide; alkali metalhydroxides, such as potassium hydroxide; alkali earth metal oxides, suchas magnesium oxide; alkali earth metal hydroxides, such as calciumhydroxide; transition metal oxides, such as titanium oxide and zincoxide; transition metal hydroxides; post-transition metal oxides, suchas aluminum oxide; and post-transition metal hydroxides (i.e. for allsizes of the stabilizing agents) to an aqueous fluid gelled with a VESmay increase the ability of the fluid to suspend solids, may indirectlyreduce the viscosity of the fluid, may reduce the rate of fluid leak-offinto the reservoir, may improve the thermal stability of the fluid'sviscosity, and may prevent or inhibit the precipitation-like phaseseparation of the viscoelastic surfactant by improving its hightemperature aqueous solubility, and combinations of these effects. Inparticular, the VES-gelled aqueous fluids containing these agents may bemore stable at high temperatures, such as at 200° F. (93° C.) or higher.This discovery allows the VES system to be used at a higher temperature,and helps minimize formation damage after hydraulic fracturingoperations. The introduction of these additives to the VES systems couldalso possibly lower the amount of VES surfactant needed to obtain thestable fluid viscosity necessary to perform VES applications ortreatments, particularly since less of the VES is lost due to oil-likephase separation, thermal degradation precipitation, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, and 5B are photographs of two13.0 ppg (1.6 kg/liter) CaCl₂/CaBr₂ brines containing 4% by volume (bv)WG-3L VES surfactant, with 0.077% by weight (bw) 30 nm ZnO additive(Fluid A on left) and without (Fluid B on right) at increasingly longtime intervals;

FIG. 6 is a graph of fluid viscosity over time for a base fluid of 13.0ppg (1.6 kg/liter) CaCl₂/CaBr₂ brines containing 4% by volume (bv) WG-3LVES surfactant measured at 250° F. (121° C.) and 100 1/s both with andwithout 6 pptg (0.7 kg/m³) nano-sized ZnO particles; and

FIG. 7 is a graph of fluid viscosity over time for a base fluid of 13.0ppg (1.6 kg/liter) CaCl₂/CaBr₂ brines containing 4% by volume (bv) WG-3LVES surfactant measured at 80° F. (27° C.) and different shear ratesboth with and without 0.077% bw 30 nm-sized ZnO particles.

DETAILED DESCRIPTION

It has been discovered that the addition of a small amount ofnanoparticles in viscoelastic surfactant micellar fluids may effectivelysuspend solids therein for uniform distribution, for instance for thedistribution of proppant in a fracture in hydraulic fracturing, for highgravel loading in gravel packing and frac-packing, for carrying drillingdebris in drilling operations, and for high solids loading for wastedisposal. Nanoparticles, such as nano-sized zinc oxide (ZnO), associatewith surfactant micelles in aqueous viscoelastic surfactant solutions tobuild networks to prevent the carried solids from settling. As will bediscussed below, lab testing shows that adding 0.07 percent bw 30nanometer (nm) ZnO particles into VES-gelled surfactant solutions maysuspend 1 pound per gallon (ppg) (0.1 kg/liter) 20/40 mesh (850-425micron) high density ceramic proppant for 90 minutes without noticeableproppant settling. This is contrasted with the proppant settling to thebottom of a glass bottle within 10 minutes in an otherwise identical VESsolution without adding the nanoparticles.

More specifically with respect to hydraulic fracturing treatments ofunderground oil and gas bearing formations, there are typically twostages of fluid pumping. In the first stage, a fluid that does not carryproppant is pumped to crack the formation and create fractures. In thesecond stage, proppant-carrying fluid is pumped into the fractures andtransports proppant into the open fractures. During the pumping andfracture closure, the proppant settling rate has a remarkable influenceon the final propped fracture geometry and well productivity increase.If the proppant settles too quickly, this causes the proppant toconcentrate at the bottom part of the fractures before they close. Theupper parts of the fractures will consequently close on little or noproppant, which generates little increased productivity by thefracturing treatment. The methods and compositions herein providetechniques and fluids for helping keep the proppant (and other solids)suspended during the second hydraulic fracturing step so that theproppant is uniformly distributed throughout the fractures.

Magnesium oxide particles and powders have been used as stabilizers forVES-gelled aqueous fluids at temperatures from about 180 to about 300°F. (about 82 to about 149° C.) as disclosed in U.S. patent applicationSer. No. 11/125,465 (U.S. Patent Application Publication No.2005/0252658 A1). However, it has been discovered that nano-sizedparticles of alkali earth metal oxides, alkali earth metal hydroxides,alkali metal oxides, alkali metal hydroxides, transition metal oxides,transition metal hydroxides, post-transition metal oxides, andpost-transition metal hydroxides, and mixtures thereof have particularadvantages for improving the suspension of solids, e.g. proppants in onenon-limiting example, in a VES-gelled aqueous fluid.

It will be appreciated that although MgO and ZnO particles are notedthroughout the application herein as representative or suitable types ofalkali earth metal oxide and/or alkali earth metal hydroxide particle,other alkali earth metal oxides and/or alkali earth metal hydroxidesand/or transition metal oxides, transition metal hydroxides,post-transition metal oxides, and post-transition metal hydroxides, maybe used in the methods and compositions herein. Additionally, the alkalimetal oxides and/or hydroxides may be used alone or in combination withthe alkali earth metal oxides and hydroxides, and/or together with oneor more transition metal oxide, transition metal hydroxide,post-transition metal oxide, and post-transition metal hydroxide.

By “post-transition metal” is meant one or more of aluminum, gallium,indium, tin, thallium, lead and bismuth. In another non-limitingembodiment herein, the nano-sized particles are oxides and hydroxides ofelements of Groups IA, IIA, IVA, IIB and IIIB of the previous IUPACAmerican Group notation. These elements include, but are not necessarilylimited to, Na, K, Mg, Ca, Ti, Zn and/or Al.

In a specific instance, a post-transition metal oxide, ZnO, has beenfound to improve the ability of VES fluids to suspend proppants, as theZnO test data show in the Examples.

The nano-sized MgO and ZnO particles are suspected of having additionalchemistry useful for VES proppant improving ability. Without beinglimited to any one particular theory, it is suspected that somenano-sized MgO and ZnO particles have unique particle charges that usechemisorption, crosslinking and/or other chemistries to associate andstabilize the VES micelles. This technical improvement is helpful in thefield when applying the MgO and ZnO additive technology, to assureVES-gelled proppant suspension.

The solid particulates and powders useful herein include, but are notnecessarily limited to, slowly water-soluble alkali earth metal oxidesor alkali earth metal hydroxides, or mixtures thereof. In onenon-limiting embodiment, the alkali earth metal in these additives mayinclude, but are not necessarily limited to, magnesium, calcium, barium,strontium, combinations thereof and the like. In one non-limitingembodiment, MgO may be obtained in high purity of at least 95 wt %,where the balance may be impurities such as Mg(OH)₂, CaO, Ca(OH)₂, SiO₂,Al₂O₃, and the like.

In another non-limiting embodiment, the particle size of the additivesand agents ranges between about 1 nanometer independently up to about500 nanometers. In another non-limiting embodiment, the particle sizeranges between about 5 nanometers independently up to about 100nanometer. In another non-restrictive version, the particles may have amean particle size of about 10 nm or more, alternatively about 50 nm orless, and in another possible version about 40 nm or less.

The amount of nano-sized particles in the VES-gelled aqueous fluid mayrange from about 0.1 to about 50 pptg (about 0.01 to about 6 kg/1000liters). Alternatively, the lower threshold of the proportion range maybe about 1.0 pptg (about 0.1 kg/1000 liters), while the upper thresholdof proportion of the particles may independently be about 20 pptg (about2.4 kg/1000 liters) pptg. Thus far, the proportion of nanoparticles hasnot been noticed as tied to the solids loading in the fluid.

The nano-sized particles herein may be added along with the VES fluidsprior to pumping downhole or other application. The VES-gelled aqueousfluids may be prepared by blending or mixing a VES into an aqueousfluid. The aqueous base fluid could be, for example, water, brine,aqueous-based foams or water-alcohol mixtures. The brine base fluid maybe any brine, conventional or to be developed which serves as a suitablemedia for the various concentrate components for carrying solids. As amatter of convenience, in many cases the brine base fluid may be thebrine available at the site used in the completion fluid (for completinga well) or other application, for a non-limiting example.

More specifically, and in non-limiting embodiments, the brines may beprepared using salts including, but not necessarily limited to, NaCl,KCl, CaCl₂, MgCl₂, NH₄Cl, CaBr₂, NaBr₂, sodium formate, potassiumformate, and other commonly used stimulation and completion brine salts.The concentration of the salts to prepare the brines may be from about0.5% by weight of water up to near saturation for a given salt in freshwater, such as 10%, 20%, 30% and higher percent salt by weight of water.The brine may be a combination of one or more of the mentioned salts,such as a brine prepared using NaCl and CaCl₂ or NaCl, CaCl₂, and CaBr₂as non-limiting examples. In another non-limiting example, the use ofthe nanoparticles of this invention may work better in the highersalinity brines, such as 20% to 30% and higher salt by weight of water,particularly as fluid temperature increases.

The viscoelastic surfactants suitable for use herein include, but arenot necessarily limited to, non-ionic, cationic, amphoteric, andzwitterionic surfactants. Specific examples of zwitterionic/amphotericsurfactants include, but are not necessarily limited to, dihydroxylalkyl glycinate, alkyl ampho acetate or propionate, alkyl betaine, alkylamidopropyl betaine and alkylimino mono- or di-propionates derived fromcertain waxes, fats and oils. Quaternary amine surfactants are typicallycationic, and the betaines are typically zwitterionic. The thickeningagent may be used in conjunction with an inorganic water-soluble salt ororganic additive such as phthalic acid, salicylic acid or their salts.

Some non-ionic fluids are inherently less damaging to the producingformations than cationic fluid types, and are more efficacious per poundthan anionic gelling agents. Amine oxide viscoelastic surfactants havethe potential to offer more gelling power per pound, making it lessexpensive than other fluids of this type.

The amine oxide gelling agents RN⁺(R′)₂O⁻ may have the followingstructure (I):

where R is an alkyl or alkylamido group averaging from about 8 to 24carbon atoms and R′ are independently alkyl groups averaging from about1 to 6 carbon atoms. In one non-limiting embodiment, R is an alkyl oralkylamido group averaging from about 8 to 16 carbon atoms and R′ areindependently alkyl groups averaging from about 2 to 3 carbon atoms. Inan alternate, non-restrictive embodiment, the amine oxide gelling agentis tallow amido propylamine oxide (TAPAO), which should be understood asa dipropylamine oxide since both R′ groups are propyl.

Materials sold under U.S. Pat. No. 5,964,295 include ClearFRAC™ whichmay also comprise greater than 10% of a glycol. This patent isincorporated herein in its entirety by reference. One useful VES is anamine oxide. As noted, a particularly preferred amine oxide is tallowamido propylamine oxide (TAPAO), sold by Baker Oil Tools as SurFRAQ™VES. SurFRAQ is a VES liquid product that is 50% TAPAO and 50% propyleneglycol. These viscoelastic surfactants are capable of gelling aqueoussolutions to form a gelled base fluid. The additives of this inventionmay also be used in Diamond FRAQ™ which is a VES system, similar toSurFRAQ, which contains VES breakers sold by Baker Oil Tools.

The amount of VES included in the fracturing fluid, as one non-limitingembodiment of a treatment fluid herein, depends on two factors. Oneinvolves generating, creating or producing enough viscosity to controlthe rate of fluid leak off into the pores of the fracture, which is alsodependent on the type and amount of fluid loss control agent used, andthe second involves creating, generating or producing a viscosity highenough to develop the size and geometry of the fracture within thereservoir for enhanced reservoir production of hydrocarbons and to alsokeep the proppant particles suspended therein during the fluid injectingstep, in the non-limiting case of a fracturing fluid. As describedherein, the nano-sized particulate additives have been found to helpwith suspending solids such as proppants. Thus, depending on theapplication, the VES is added to the aqueous fluid in concentrationsranging from about 0.5 to 12.0% by volume of the total aqueous fluid (5to 120 gallons per thousand gallons (gptg)). In another non-limitingembodiment, the proportion range herein may be from about 1.0 to about6.0% by volume VES product. In an alternate, non-restrictive embodiment,the amount of VES ranges from 2 to about 10 volume %.

In application, the ZnO or MgO (or other particulate) additives may bemixed with the VES-gelled fluids at the surface in any order with thesolids and the VES before they are pumped downhole. Of course, in theembodiment where the nanoparticle additives are helping suspend drillingdebris during drilling operations, no solids are in the VES-gelledfluids containing the nanoparticle additives being injected into thewellbore, but the fluid encounters and suspends the drilling debrisdownhole and transports it out of the hole. Similarly, when thecompositions described herein are used for waste disposal, such as inore processing in one non-limiting embodiment, they are pumped to anarea where solids are encountered and suspended for transport to removaland disposal zones. In another non-limiting embodiment, solid waste orashes from power generation plants can be suspended and injected into anunderground formation for disposal. In still another non-limitingembodiment, natural occurring radioactive material (NORM), such asscale, is often removed from wellbore tubing and casing can be suspendedand injected into an underground formation for disposal.

It is expected that high solids loadings may be achieved with thecompositions of this invention, for instance, up to about 20 pounds pergallon (2.4 kg/liter) fluid solids loading. Thus far, the researchershave not seen that the nanoparticles' loading is directly tied to thequantity of the solids loading, e.g. proppants. In one non-limitingexplanation, the nanoparticles' pseudo-crosslinking of the VES micellesis thought to build network structures inside the VES-gelled fluid tohold or suspend the proppant from quick settling, possibly byassociating the worm-like or elongated micelles together. The size ofthe solids being suspended may range from about 100 mesh to about 8 mesh(about 150 to about 2,360 microns).

In hydraulic fracturing applications, propping agents are typicallyadded to the base fluid after the addition of the VES. Propping agentsinclude, but are not limited to, for instance, quartz sand grains, glassand ceramic beads, bauxite grains, sintered bauxite, sized calciumcarbonate, other sized salts, walnut shell fragments, aluminum pellets,nylon pellets, and the like. Gravel used for screens may also be ofsimilar materials. The propping agents are normally used inconcentrations between about 1 to 14 pounds per gallon (120-1700 kg/m³)of fracturing fluid composition, but higher or lower concentrations maybe used as the fracture design requires. A typical proppant size is20/40 mesh (from 850 to 425 microns), although of course other sizes maybe employed. The base fluid may also contain other conventionaladditives common to the well service industry such as water wettingsurfactants, non-emulsifiers and the like. In the methods andcompositions herein, the base fluid may also contain additives which maycontribute to breaking the gel (reducing the viscosity) of the VESfluid.

While the viscoelastic fluids herein are described most typically hereinas having use in fracturing fluids, it is expected that they will findutility in completion fluids, gravel pack fluids, fluid loss pills, lostcirculation pills, diverter fluids, foamed fluids, stimulation fluids,water and/or gas control fluids, enhanced oil recovery (i.e. tertiaryrecovery) fluids, and the like.

In another non-restrictive embodiment, the treatment fluid may containother viscosifying agents, other different surfactants, claystabilization additives, scale dissolvers, biopolymer degradationadditives, and other common and/or optional components.

In a particularly useful embodiment herein, use of these particulateadditives with internal VES breakers, such as polyenoic acid, may havesynergistic clean-up effects for the nano size particle-containing VESfluid. The nano-sized particle particulate agents may reduce or inhibitoil-like phase separation of the leaked-off VES fluids within thereservoir pores and with internal breaker present to reduce theleaked-off VES fluid's viscosity more rapid and possibly more completeVES fluid removal may be achieved, with return permeability as high as90% and greater.

The invention will be further described with respect to the followingExamples which are not meant to limit the invention, but rather tofurther illustrate the various embodiments.

Example 1 Proppant Settling Tests

It is the nanoparticles associating with VES micelles in VES solutionsthat are believed to build relatively strong networks for high proppantloading, in one non-limiting embodiment, and thus uniformly distributeproppant into the fracture, thus avoiding quick proppant settling at thebottom of the fracture. In this Example 1, two fluids were prepared:

-   Fluid A: 13.0 ppg (1.6 kg/I) CaCl₂/CaBr₂ brine containing 4% by    WG-3L VES surfactant, with 0.077% bw 30 nm ZnO particulate additive    (product #30N0801 available from Inframat Advanced Materials).-   Fluid B: 13.0 ppg (1.6 kg/I) CaCl₂/CaBr₂ brine containing 4% by    WG-3L VES surfactant, with no nanoparticles.

One hundred (100) milliliters of both Fluids A and B were mixed eachwith 12 grams 20/40 mesh (850-425 micron) proppant (CarboHSP highstrength ceramic proppant, available from Carbo Ceramics) separately. Atthe same, both of the mixed fluids were poured into two glass bottlesand photographs were taken at different times. In all photographs, FIGS.1-5, Fluid A is on the left and Fluid B is on the right.

The photograph of FIG. 1 was taken 1 minute after pouring and theproppants in both fluids appear fully suspended.

The photograph of FIG. 2 was taken 10 minutes after pouring, and it maybe readily seen that the proppant in Fluid B has substantially settled.

The photograph of FIG. 3 was taken 20 minutes after pouring, and it maybe seen that the proppant in Fluid B has settled further from that shownin the photograph of FIG. 2.

The photograph of FIG. 4 was taken 30 minutes after pouring, and it maybe seen that the proppant in Fluid B has settled somewhat further fromthat shown in the photograph of FIG. 3, while the proppant in Fluid A onthe left was still suspended.

Finally, the photograph of FIG. 5 was taken 90 minutes after pouring,and it may be seen that the proppant in Fluid B has completely settledas compared with the proppant in Fluid A on the left which was stillsuspended substantially as it was when it was just poured (FIG. 1A).

Example 2

Shown in FIG. 6 is a graph of fluid viscosity over time for a base fluidof 13.0 ppg (1.6 kg/liter) CaCl₂/CaBr₂ brines containing 4% by volume(bv) WG-3L VES surfactant measured at 250° F. (121° C.) and 100 1/s. Thebase fluid without 6 pptg (0.7 kg/m³) nano-sized ZnO particles is thelower curve denoted by the gray triangles; the base fluid with 6 pptg(0.7 kg/m³) nano-sized ZnO particles is the upper curve denoted by theblack diamonds. This graph shows a large difference between the twofluids, one with and without nanoparticles, at a high temperature. Thisdata demonstrate that the use of the method and compositions herein maybe effective at high temperature.

Example 3

FIG. 7 presents a graph of fluid viscosity over time for a base fluid of13.0 ppg (1.6 kg/liter) CaCl₂/CaBr₂ brines containing 4% by volume (bv)WG-3L VES surfactant measured at 80° F. (27° C.) and different shearrates both with and without 0.077% bw 30 nm-sized ZnO particles. Thecurve for the fluid with the nano-sized ZnO particles is shown by graysquares, and the fluid without nanoparticles is shown by black diamonds.This data demonstrate that for very low shear rates, the VES-gelledcompositions herein containing nanoparticles have more than 10 timeshigher viscosity than the VES-gelled fluid without nanoparticles. Athigher shear rates, the viscosities are essentially the same.

In the foregoing specification, it will be evident that variousmodifications and changes may be made thereto without departing from thebroader spirit or scope of the invention as set forth in the appendedclaims. Accordingly, the specification is to be regarded in anillustrative rather than a restrictive sense. For example, specificcombinations of viscoelastic surfactants with certain solids andparticular additives such as alkali earth metal oxides, alkali earthmetal hydroxides, alkali metal oxides, alkali metal hydroxides,transition metal oxides, transition metal hydroxides, post-transitionmetal oxides, and post-transition metal hydroxides, of various sizes,brines, viscoelastic surfactants, and other components falling withinthe claimed parameters, but not specifically identified or tried in aparticular composition, are anticipated to be within the scope of thisinvention. In another non-limiting embodiment, the compositions andmethods herein may find utility in delivering ZnO, MgO and similarmaterials in the fields of solid waste handling and disposal.

The words “comprising” and “comprises” as used throughout the claims areto be interpreted as “including but not limited to”.

What is claimed is:
 1. A gelled aqueous fluid comprising: an aqueousbase fluid; a viscoelastic surfactant (VES) gelling agent; a particulateadditive having a mean particle size of from about 1 nm to about 500 nmor less, selected from the group consisting of alkali earth metaloxides, alkali earth metal hydroxides, alkali metal oxides, alkali metalhydroxides, transition metal oxides, post-transition metal oxides, andmixtures thereof, where the transition metal in the transition metaloxide is titanium, and where the post-transition metal in thepost-transition metal oxide is selected from the group consisting ofgallium, indium, thallium, lead and bismuth; and solids selected fromthe group consisting of proppants, gravel, drilling debris, wastesolids, and combinations thereof, and wherein the size of the solidsranges from about 100 mesh to about 8 mesh (about 150 to about 2,360microns); where the particulate additive is present in an amounteffective to suspend the solids in the gelled aqueous fluid.
 2. Thegelled aqueous fluid of claim 1 where the aqueous base fluid is brine.3. The gelled aqueous fluid of claim 1 where: the alkali earth metal isselected from the group consisting of magnesium, calcium, strontium,barium and mixtures thereof; and the alkali metal is selected from thegroup consisting of lithium, sodium, potassium, and mixtures thereof. 4.The gelled aqueous fluid of claim 1 where the effective amount of theadditive ranges from about 0.1 to about 50.0 pptg (about 0.01 to about 6kg/1000 liters) based on the gelled aqueous fluid.
 5. The gelled aqueousfluid of claim 1 where the solids range in size from about 100 mesh toabout 8 mesh (about 150 to about 2,360 microns).
 6. The gelled aqueousfluid of claim 1 where the solids loading is equal to or less than 20lbs per gallon (2.4 kg/liter).
 7. A gelled aqueous fluid comprising: anaqueous brine base fluid; a viscoelastic surfactant (VES) gelling agent;and from about 0.1 to about 50.0 pptg (about 0.01 to about 6 kg/1000liters) based on the gelled aqueous fluid of a particulate additivehaving a mean particle size of from about 1 nm to about 100 nm or less,selected from the group consisting of alkali earth metal oxides, alkaliearth metal hydroxides, alkali metal oxides, alkali metal hydroxides,transition metal oxides, post-transition metal oxides, and mixturesthereof, where the transition metal in the transition metal oxide istitanium, and where the post-transition metal in the post-transitionmetal oxide is selected from the group consisting of gallium, indium,thallium, lead and bismuth; and solids selected from the groupconsisting of proppants, gravel, drilling debris, waste solids, andcombinations thereof, and wherein the size of the solids ranges fromabout 100 mesh to about 8 mesh (about 150 to about 2,360 microns). 8.The gelled aqueous fluid of claim 7 where: the alkali earth metal isselected from the group consisting of magnesium, calcium, strontium,barium and mixtures thereof; and the alkali metal is selected from thegroup consisting of lithium, sodium, potassium, and mixtures thereof. 9.The gelled aqueous fluid of claim 7 where the solids range in size fromabout 100 mesh to about 8 mesh (about 150 to about 2,360 microns). 10.The gelled aqueous fluid of claim 7 where the solids loading is equal toor less than 20 lbs per gallon (2.4 kg/liter).
 11. A gelled aqueousfluid comprising: an aqueous brine base fluid; a viscoelastic surfactant(VES) gelling agent; and from about 0.1 to about 50.0 pptg (about 0.01to about 6 kg/1000 liters) based on the gelled aqueous fluid of aparticulate additive having a mean particle size of from about 1 nm toabout 100 nm or less, selected from the group consisting of alkali earthmetal oxides, alkali earth metal hydroxides, alkali metal oxides, alkalimetal hydroxides, transition metal oxides, post-transition metal oxides,and mixtures thereof, where the alkali earth metal is selected from thegroup consisting of magnesium, calcium, strontium, barium and mixturesthereof; and the alkali metal is selected from the group consisting oflithium, sodium, potassium, and mixtures thereof; the transition metalin the transition metal oxide is titanium, and the post-transition metalin the post-transition metal oxide is selected from the group consistingof gallium, indium, thallium, lead and bismuth; and solids selected fromthe group consisting of proppants, gravel, drilling debris, wastesolids, and combinations thereof, and wherein the size of the solidsranges from about 100 mesh to about 8 mesh (about 150 to about 2,360microns), where the solids range in size from about 100 mesh to about 8mesh (about 150 to about 2,360 microns).
 12. The gelled aqueous fluid ofclaim 11 where the solids loading is equal to or less than 20 lbs pergallon (2.4 kg/liter).